Investigation on the Surface‐Confined Self‐Assembly Stabilized by Hydrogen Bonds of Urea and Amide Groups: Quantitative Analysis of Concentration Dependence of Surface Coverage

Formation of a hydrogen‐bond network via an amide group is a key driving force for the nucleation–elongation‐type self‐assembly that is often seen in biomolecules and artificial supramolecular assemblies. In this work, rod‐coil‐like aromatic compounds bearing an amide ( 1 a – 3 a ) or urea group ( 1 u – 3 u ) were synthesized, and their self‐assemblies on a 2‐D surface were investigated by scanning tunneling microscopy (STM). According to the quantitative analysis of the concentration dependence of the surface coverage, it was revealed that the strength of the hydrogen bond (i.e., amide or urea) and the number of non‐hydrogen atoms in a molecular component (i.e., size of core and length of alkyl side chain) play a primary role in determining the stabilization energy during nucleation and elongation processes of molecular ordering on the HOPG surface.     

Synthesis and Crystal Structure of p-tert-Butylthiacalix[8]arene: A New Member of Thiacalixarenes

Even though it was obtained in poor yield, p-tert-butylthiacalix[8]arene (TC8A) has been synthesized as a new member of thiacalix[n]arenes by the terephthalate-induced cyclization of a mixture of acyclic oligomers, which was obtained by the reaction between p-tert-butylphenol and sulfur with CaO in ethylene glycol/diphenyl ether system. Slow evaporation of the chloroform solution of TC8A afforded guest-free crystals consisting of TC8A itself. The close-packed crystal structure of TC8A resembles that of p-tert-butylcalix[8]arene (C8A) closely, containing a plated loop molecular structure.This revised version was published online in July 2005 with a corrected issue number.     

Microwave-resonance-induced resistivity: evidence of ultrahot surface-state electrons on liquid 3He

Measurements of the dc resistivity of surface-state electrons on liquid helium exposed to microwave radiation are reported. It is shown that the resonant microwave excitation of surface-state electrons is accompanied by a strong increase in their resistivity, which is opposite to the result expected from the previously used two-level model. We show that even a very small fraction of electrons excited to the first excited state and decaying back due to vapor-atom scattering strongly heat the electron system, causing a population of higher subbands. The calculated resistivity change is in good agreement with the observed data.     

Die Löslichkeit von aromatischen Verbindungen mit polaren Gruppen in Wasser

Zusammenfassung Die Löslichkeiten folgender Verbindungen wurden in Wasser bei 5°-Intervallen von 0° bis 40° bestimmt; Anilin, Mtrobenzol, Chlorbenzol,-Oxynaphthalin und-Nitronaphthalin. Aus diesen Ergebnissen wurden die thermodynamischen Parameter für den Lösungsprozeß der reinen flüssigen Verbindungen in Wasser berechnet. Das Resultat wurde mit Hilfe des Begriffs der Eisberge erklärt.Beim Benzol, Anilin und Chlorbenzol waren die Lösungswärmen negativ bei niedrigeren Temperaturen und wurden mit steigender Temperatur positiver. Dagegen traten beim Nitrobenzol,-Oxynaphthalin und-Nitronaphthalin stets die positiven Lösungswärmen auf. Dies sollte auf die großen intermolekularen Kräfte in der reinen Flüssigkeit zurückzuführen sein.     

Quantum statistical hierarchy equation in nonequilibrium systems

An extension is given for the Fourier expansion method with the contraction technique, which was introduced by Balescu for quantum statistical systems. This is attained by introducing a diagrammatic method with a concept of moving contraction. Then the hierarchy equation for the Contracted Fourier coefficient of the Wigner distribution function is obtained. As an application, a generalized master equation involvingn-body collision effects and quantum statistical effects is also derived.     

Time-resolved Fourier-transform infrared reflection study on photoinduced phase transition of tetrathiafulvalene-p-chloranil crystal

We have measured temporal change of infrared reflection spectrum of ionic phase oftetrathiafulvalene-p-chloranil (TTF-CA) crystal induced by 10 ns pulsedlaser excitation at 2.35 eV with using a step-scan Fourier-transform infraredspectrometer. The excitation reduced the magnitude of thea _g -mode bands around 980 cm^-1and 1380 cm^-1 and enhanced reflection intensity at 1630 cm^-1. Thetime evolution of both the a _g -mode changes and the enhancementat 1630 cm^-1 are described by the sum of two decay components: one decayedwithin 2 μs and the other showed very gradual decay within the timerange used in the present study. The fractional changes of reflectivity for the fast decaycomponents were almost identical for all a _g modes.The 1630 cm^-1 enhancement can be ascribed to the carbonyl stretchingvibration of CA. The position of this peak shifts slightly to low-wavenumber side from theCA peak of the neutral phase in thermal equilibrium. Consequently, the fast decaycomponent is ascribed to the photoinduced phase. The slow decay component is conceivablydue to the metastable center formed by the excitation, because we could not resolve thespectral change corresponding to the slow component in the range between 1595and 1660 cm^-1, where the carbonyl stretching vibration of TTF-CA is observed.The degree of charge transfer of the photoinduced phase is evaluated to 0.52 ± 0.08 bycomparing the peak position of the transient enhancement with those of the carbonylstretching vibration modes in ionic and neutral phases in thermal equilibrium.     

Structural phase transitions at clean and metal-covered Si(111) surfaces investigated by RHEED spot analysis

Structural phase transitions between various kinds of superlattice structures formed on a Si(111) surface have been investigated by spot analysis of reflection high-energy electron diffraction (RHEED). Reversible transitions induced by temperature changes and irreversible ones induced by metal depositions were observed. Detailed discussions on the dynamics of the phase transitions are made by quantitative analyses of integrated spot intensity and profile. For a phase transition of 7′7  1′1 structures on a clean Si(111) surface, a hysteresis with temperature difference of 5°C. between in heating and cooling processes was found in the spot intensity change, indicating a first-order transition. Hysteresis was hardly recognized, on the other hand, for transitions of Au-induced superstructures (5×2-Au or ×-Au)  1×1-Au. The spot profiles were found to be broadened during the transition of Si(111)-×-Au  1×1-Au, which was a signature of a continuous transition, while the profiles remained unchanged during the transitions of the 7×7  1×1 and 5×2-Au  1×1-Au phases. Structural conversions induced by In adsorption on the Si(111) surface kept at constant temperatures were also analyzed. The conversions at room temperature were totally dependent on the initial substrate surface structures; the 7×7 surface did not show any structural conversion with In adsorption, while the ×-In surface successively converted to a 2×2 and a × phase with coverage increase. The structural transitions at elevated temperatures were sensitively dependent on the temperatures. Sequences of transitions among the 7×7, 4×1, ×, 1×, and ×4 were quantitatively revealed as changes in RHEED spot intensity.     

Investigating How Organic Solvents Affect Tissue Culture Polystyrene Surfaces through Responses of Mesenchymal Stem Cells

Polymer coating of tissue culture polystyrene (TCPS) surfaces promotes their biofunctionality, which can aid manipulation of cellular functions. However, the effect of the solvent used for polymer coating is yet to be elucidated. In this study, solvent‐treated TCPS surfaces using water, methanol, ethanol, 2‐propanol, and dimethyl sulfoxide are fabricated. Solvent treatment of TCPS surfaces is performed by spreading solvents onto the surfaces and allowing them to dry. Solvent treatment changes the surface roughness and wettability, depending on the kind of solvents. In addition, these surface property changes affected the extension, proliferation, and differentiation of human bone marrow–derived mesenchymal stem cells. These results suggest that solvent selection for polymer coating is crucial in the regulation of cell responses. Further, treatment with an appropriate solvent can result in a more suitable culture environment for modulating cellular functions.     

Efficient CO2 Removal for Ultra‐Pure CO Production by Two Hybrid Ultramicroporous Materials

Removal of CO₂ from CO gas mixtures is a necessary but challenging step during production of ultra‐pure CO as processed from either steam reforming of hydrocarbons or CO₂ reduction. Herein, two hybrid ultramicroporous materials (HUMs), SIFSIX‐3‐Ni and TIFSIX‐2‐Cu‐i , which are known to exhibit strong affinity for CO₂, were examined with respect to their performance for this separation. The single‐gas CO sorption isotherms of these HUMs were measured for the first time and are indicative of weak affinity for CO and benchmark CO₂/CO selectivity (>4000 for SIFSIX‐3‐Ni ). This prompted us to conduct dynamic breakthrough experiments and compare performance with other porous materials. Ultra‐pure CO (99.99 %) was thereby obtained from CO gas mixtures containing both trace (1 %) and bulk (50 %) levels of CO₂ in a one‐step physisorption‐based separation process.